Three-dimensional polycyclic bisphenol polycarbonates and polyesters



United States Patent US. Cl. 260-619 15 Claims ABSTRACT OF THEDISCLOSURE New bisphenols [such as 4,4-(2-norbornylidene)diphenol, etc.]containing a saturated polycyclic threedimensional structure whichincludes a saturated bicyclic atomic-bridged hydrocarbon ring member aredisclosed which can be used to prepare new polymers having improvedtemperature properties and solubility in volatile solvents.

This application is a'division of Caldwell and Jackson U.S. Ser. No.292,139; filed July 1, 1963 and now US. Pat. 3,317,466, which in turn isa continuation-in-part of Caldwell and Jackson.U.S. Ser. No. 137,980,filed Sept. 14, 1961, and now abandoned.

This invention relates to polycarbonates and polyesters from newbisphenols. More specifically, this invention relates to novelthermoplastic polycarbonates and polyesters which are valuable in theproduction of films, filaments, and shaped articles having excellenthigh-temperature properties and solubility in low-boiling solvents.

During the past few years many new bisphenol polycarbonates andpolyesters have been reported. Polycarbonates have been described bySchnell, Agnew, Chern.,

68, 633-660 (1956) and Ind. Eng. Chem, 51, 157-160 (1959). Polyestershave been described 'by Eareckson, J. Poly. Sc., 40, 399-405 (1959), andother examples are found in many U.S. patents such as 2,035,578 and2,595,- 343 and in various foreign patents such as British Pats.621,102, 636,429 and 648,513. Compared to these reported polymers, thenew bisphenol polycarbonates and polyesters of this invention haveappreciably higher softening temperatures, second-order transitiontemperatures, and heatdistortion temperatures. The new polymers alsohave higher moduli of elasticity, and they are appreciably more solublein volatile solvents such as methylene dichloride, chloroform, andbenzene. Solubility in these solvents is a distinct advantage, becausemany of the polymers melt too high to extrude into films or fibers; thefilms can be obtained, however, by casting from solution and the fibersby wetor dry-spinning from solution.

The invention has for its principal object to provide novelpolycarbonate and polyester compositions which are soluble inlow-boiling solvents and which have exceptionally high softeningtemperatures, second-order transition temperatures, and heat-distortiontemperatures.

Another object is to provide novel polycarbonate and polyestercompositions which have high moduli of elasticity.

Another object is to provide novel polycarbonate and polyestercompositions which are especially adapted to the manufacture of fibers,yarns, films, and other shaped objects having excellent electricalproperties and tensile properties at temperatures up to 200 C. andhigher.

Other objects will appear hereinafter.

Briefly stated, the invention comprises novel polycarbonates and otherpolyesters from certain bisphenols and the novel bisphenols. Theparticular polymers of this invention are condensed from bisphenols inwhich the bivalent connecting radical of the bisphenol contains aPatented June 23, 1970 three-dimensional polycyclic structure containingan atomic bridge. In all of the bisphenols which characterize theinvention, the two phenol groups are attached to a single carbon atom ofthe bivalent connecting radical. Bisphenols having this linkage can becalled gem-bisphenols.

The linear polymers of the invention include polyesters of carbonicacid, called polycarbonates, and polyesters of dicarboxylic acids, whichcan be called dicarboxylic acid polyesters to distinguish them from thepolycarbonates.

The diol constituents which characterize the linear polycarbonates andpolyesters of the invention are condensation residues of bisphenolshaving the general formula:

wherein R" is hydrogen, halogen, or alkyl groups (C to C and Xrepresents a saturated gem-bivalent connecting radical containing asaturated polycyclic structure which includes a bicyclic membercontaining at least one atomic bridge.

Typical of some three-dimensional polycyclic structures is thenorbornane ring. The conventional method of drawing this ring is asfollows:

An approximate representation which shows the threedimensional nature ofthe ring is as follows:

Within the gem-bivalent connecting radical, the single carbon atom towhich the two phenol nuclei of the hisphenol are connected may be acarbon within the polycyclic structure, or it may be a group attached tothe polycyclic structure. In 4,4-(2- norbornylidene)diphenol, thephenolic groups are attached directly to a carbon atom within thepolycyclic structure:

In 4,4-(Z-norbornylmethylene)diphenol, a methylidyne group attached tothe polycyclic structure carries the phenolic groups:

The atomic bridge Within the polycyclic structure may have more than onecarbon atom, e.g., (bicyclo[2.2.2]octane) There may be more than onebridge in the polycyclic structure: e.g., (tricyclo[2.2.1.0 ]heptane)(adamantane) The atomic bridge may consist of an oxygen or nitrogen atominstead of carbon: e.g., (7-oxabicyclo[2.2.1] heptane) There may bealkyl, aryl and halide substituents on the polycyclic structure: e.g.,(substituted norborane) (hexahydro-4,7-methanoindane)(octahydro-4,7-methanoisobenzofurane) There may be additional bridges inthe fused rings,

e.g., (decahydro-1,4,5,8-dimethanonaphthalene) (dodecahydro 4,9,5,8dimethano-l-cyclopenta(b)naphthalene) Additional saturated rings may bejoined in the polycyclic structure by spiro-union linkage, e.g.,

(spiro [cyclopropane-1,7'-norbornane] Linear polycarbonates can beprepared by condensation of phosgene or a bischloroformate of a diol, ora mixture of these, with one or more diols including the novelthree-dimensional polycyclic bisphenols. It will be apparent that thepolycarbonates formed by condensing either phosgene or diolbischloroformates with the same or different diols, can be described asconsisting essentially of recurring residues of carbonic acid and thediols. By condensing the bischloroformate of one diol with another diol,homogeneous polycarbonates having regularly recurring residues will beobtained, whereas copolycarbonates will be obtained having randomlyrecurring residues when a mixture of diols are condensed with phosgene.

Linear dicarboxylic acid polyesters can be prepared by condensation ofone or more organic dicarboxylic acids, or dicarboxylic acid diesters,with one or more diols including at least in part one of the polycyclicbisphenols contemplated by the present invention. By whatevercondensation process the polyesters are formed they can be described aspolymers consisting essentially of condensation residues of dicarboxylicacids and diols.

According to the invention, at least 10 mole percent (preferably atleast 35 percent) of the linear condensation polymer is composedessentially of residues of one of the novel bisphenols having abridged-polycyclic-ring structure in the gem-bivalent connecting radicalof the bisphenol. The invention includes mixed polymers, interpolymers,and random copolymers as well as the simpler polymers having asconstituents only one acid residue and only one bisphenol residue inrecurring groups.

Various polymers of this invention are characterized by having highheat-softening temperatures, high heat-distortion temperatures, highmoduli of elasticity, high second-order transition temperatures, andvarious other unusually valuable properties such as high degree offiexibility, improved stability, solubility in methylene chloride, highmelting points, excellent resistance to burning when chlorine is presentas a substituent, high impact strength, etc. Not all of these propertiesare present in the same degree in any given polymer; many of thesegroups of polymers are clearly distinct from one another. However, thepolymers of this invention are generally characterized by having asurprisingly excellent combination of high melting range, high modulusof elasticity, high second-order transition temperature, and highheat-distortion temperature. As a result of this invention, valuablefibers, films, molding plastics and other synthetic resinous materialscan be produced.

It would be expected in preparing polycarbonates and polyesters thatdecreasing the symmetry of a monomer and introducing big bulky sidegroups would diminish the higher temperature characteristics such asyielding a lower softening range. On the contrary, it has been foundthat the melting range and other properties of polycarbonates andpolyesters derived from bisphenols having polycyclic structures in theconnecting groups is increased as the size of the ring system increases.

It surprisingly appears that presence of the bulky group of thepolycyclic ring system exerts a chain stiffening elfect and also asolubilizing effect. Consequently the polymers are soluble in commonorganic solvents, yet still have very high melting points, highheat-distortion temperatures, high second-order transition temperatures,etc.

It has been found that in polycarbonates and polyesters containing aslittle as mole percent of the residue of one of the novel bisphenolsthere is a significant improvement in the high temperature propertiesmentioned above.

The invention provides a wide new range of polymers useful for hightemperature applications in which previously known resins would not besuitable. From the new polycarbonates and polyesters can be chosen oneor several which possess the particular properties needed. For hightemperature applications most of the new polycarbonates possess evenhigher melting ranges, heat-distortion temperatures, and second-ordertransition temperatures than previously known polycarbonates frombisphenols having aliphatic or cycloaliphatic connecting radicals. Thesame is true for polyesters from dicarboxylates provided by the inventonas compared with known polyesters having otherwise similar properties.

In mixed polycarbonates and polyesters containing a significantproportion of residues of the new polycyclic bisphenols, the hightemperature properties are improved considerably more than would be sowith other diols, even more than with the known bisphenols. Of course,differences in physical properties exist among the polymers of theinvention, depending upon the nature of the acid and diol constituentsof the polymer chain and upon the particular novel bisphenol present inthe polyester. For instance, the polycarbonates will possess manyproperties, distinctly difierent from the polydicarboxylate esters, andthere will be individual distinct diflerences in properties among thepolycarbonates, or among the polyesters of dicarboxylic acids and thevarious bisphenols of the invention. However, all of the polymers whichcontain a significant amount of one of the novel bisphenol residues,exhibit unusually good high temperature properties as mentioned above.

The inherent viscosity of the polymers should be at least as highas 0.4as measured in chloroform or other suitable solvent. For use in films,particularly for photographic film base, and for fiber applications thepolymer should have an inherent viscosity of at least 0.5 ranging upwardto about 3.0. For coatings, polymers having inherent viscosities from0.4 to 0.7 are preferred. Best results with molding or extrusioncompositions have been obtained using polymers with inherent viscositiesfrom 0.8 to 1.2.

The bisphenols used in the novel polycarbonates and polyesters of thisinvention were themselves previously unknown and had to be developed asintermediates to produce the new polycarbonates and polyesters.

PREPARATION OF BISPHENOLS The bisphenols were prepared by thecondensation of phenol or a phenolic derivative with a polycyclicaldehyde or ketone. If the ketone is 2-norbornanone and the phenoliccompound is phenol, the reaction is as follows:

Preparation of a bisphenol by condensation of phenol with acetone isdescribed in US. Pat. No. 2,468,982. The procedure there described withvarious modifications was used in preparing bisphenols in which thephenyl radicals are attached to a single carbon atom within the ringstructure, but using a polycyclic ketone rather than acetone for thecondensation reaction. Bisphenols in which the phenyl groups areattached to a methylene carbon atom attached to the polycyclic nucleuswere prepared by the condensation of a polycyclic aldehyde with aphenolic compound. The condensation reaction in which the ketone oraldehyde condenses is preferably carried out in the presence of HCl,though other acids such as sulfuric, toluenesulphonic, or methionic canbe used instead of HCl. The reaction is accelerated by heating and alsoby adding B-mercaptopropionic acid or methyl mercaptan as a catalyst.

Halogenated bisphenols are obtained in the conventional manner byhalogenation. 4,4'(2-norbornylidene)- bis[2,6-dichlorophenol] forexample, is obtained by treating the bisphenol in acetic acid with 4moles of chlorine:

A general procedure for preparing the new bisphenols from polycycliccarbonyl compounds is given in Example 1. A general procedure forchlorinating these bisphenols is given in Example 2. Later examplesdescribe the preparation of the polycyclicaldehydes and ketones, most ofwhich are reported in the literature.

Example 1 General procedure for preparing bisphenols from polycyclicaldehydes and ketones.-To a stirred mixture containing 4.0 moles of thephenolic compound, 5 ml. of S-mercaptopropionic acid, and '635 ml. ofconcentrated hydrochloric acid is added 1.0 mole of the polycycliccarbonyl compound. If the carbonyl compound is an aldehyde, it is addedslowly so that the temperature of the reaction mixture does not riseabove 40 C. Stirring of this mixture is continued several hours untilthe mixture becomes pasty. It is then allowed to stand overnight. If thecarbonyl compound is a ketone (or if the aldehyde is unreactive), themixture is stirred at 50 C. The reaction is complete when a few drops ofthe mixture is completely soluble in hot, dilute aqueous sodiumhydroxide. If over 12 hrs. is required, the reaction temperature isincreased to 75 C. and then, if necessary, until the mixture refluxes.

If the product is crystalline, it is collected on a filter and washedwith water. If it is pasty or a hard mass, the aqueous portion isdecanted and the residue stirred with hot water or benzene several timesto extract the excess phenol. If this treatment is inefiective, theexcess phenol compound is removed by steam distillation or distillationunder reduced pressure. The crystalline bisphenol is then collected,washed with water, and recrystallized. Most of the bisphenols can becrystallized from aqueous acetic acid or aqueous ethyl alcohol, butethylene dichloride containing a very small amount of ethyl alcohol ismore effective with some bisphenols.

Most of the bisphenols prepared from the polycyclic ketones and phenol(but not substituted phenols) are obtained as hydrates containing onemole of water per mole of bisphenol. A convenient way of obtaining theunhydrated compound is to dissolve the hydrated bisphenol in hotxylene-acetone, remove the water as an azeotrope, and then allow thebisphenol to crystallize.

Although the above procedure for preparing bisphenols is convenient andgenerally effective, a more rapid reaction is obtained by adding 1 moleof dry HCl to a stirred mixture of carbonyl compound (1 mole), phenoliccompound (8 moles), and B-mercaptopropionic acid ml.) at 50 C. Thisprocedure is particularly useful in the preparation of bisphenols fromsome of the polycyclic ketones containing large rings. It is alsoeffective in preparing pure bisphenols from aldehydes which tend to givesome trisphenol formation (which causes crosslinking).

Example 2 General procedure for chlorinating polycyclic bisphenols.Thebisphenol (0.50 mole) is stirred with 600- 800 ml. of acetic acid at4050 C. while chlorine is bubbled into the mixture from a lecturebottle. During the chlorine addition the bisphenol goes into solution.After 149 g. (2.1 moles) of chlorine is added, measured as the weightloss of the lecture bottle, the mixture is allowed to cool to roomtemperature. If crystallization of the product does not take place, thesolution is cooled in an ice bath. If crystallization still does notoccur, some water is added. The chlorinated bisphenol is then collected,washed with water, and dried, It is recrystallized from aqueous aceticacid or ethylene dichloride.

If the product is noncrystalline and cannot be recrystallized, it isdissolved in alcohol and converted to the disodium salt with sodiummethoxide. This salt, obtained by evaporation of the alcohol, is thenrecrystallized from a mixture of ethyl alcohol and acetone. It can beused in this form for preparing polymers by the interfacial method, orthe bisphenol can be regenerated by acidification with acetic acid.

Example 3 4,4-(2-norbornylidene)diphenols.Some of these bisphenols maybe prepared by the following synthesis:

0 c 00113 Hz HC-OCOCH; i II R )9 (IV) (V) R R=hydrogen, or one or morehalogen atoms or alkyl groups (C -C iso or normal) or aryl groupsR=hydrogen, halogen, or alkyl (C -C iso or normal) The first step is a.Diels-Alder addition between cyclopentadiene (or a substitutedcyclopentadiene) and vinyl acetate (or a substituted vinyl acetate if ahalogen atom or alkyl group is to be substituted in the 3-position ofthe norbornane ring). After hydrogenation of the double bond, thesaturated acetate (II) is hydrolyzed to the carbinol (III) and thenoxidized to the ketone (lV). When R and R are H, the ketone is callednorcamphor or l-norbornanone. Its preparation by the above synthesis isdescribed in Ann., 543 1 (1940). 2-norbornanone also may be prepared bythe hydration of norbornene (German Pat. 951,867) followed by oxidationwith chromic acid or nitric acid. Example 1 describes the preparation ofthe bisphenols (V).

4,4-(2 norbornylidene)diphenol (V, R=H, .R'=H, R=H) was obtained fromaqueous acetic acid and aqueous ethyl alcohol as a monohydrate, M.P.l77-l79 C. It also solvated with isopropyl alcohol and with ethylenedichloride when recrystallized from either of these solvents. After thesolvent was removed (see Example 1), the unsolvated bisphenol melted at199200 C.

4,4-(2 nor bornylidene)di o cresol (V, R"=H and CH,,), prepared fromnorcamphor and o-cresol (Example l), melted at 2182l9 C.

4,4 (2 norbornylidene)bis[2,6-dimethylphenol] (V, R":CH melted at 218220C.

4,4 (2 norbornylidene)bis[2,6-dichlorophen0l] (V, |R"-Cl), prepared asdescribed in Example 2, melted at l83l84 C. and gave the correctanalysis for 4 chlorine atoms per molecule.

4,4-(2-norbornylidene)bis[2-chlorophenol] (V, R=I-I and Cl) was preparedby adding 2 moles of chlorine per mole of bisphenol in the procedure ofExample 2. It melted at 163164 C. and gave the correct analysis for 2chlorine atoms per molecule.

4,4 (2 norbornylidene)bis[2,6-dibromophenol] (V, R=Br) was prepared byadding 4 moles of bromine at room temperature to 1 mole of the bisphenoldissolved in 500 ml. of methanol. Recrystallized from aqueous aceticacid, the bisphenol melted at ISO-181 C. It gave the correct analysisfor 4 bromine atoms per molecule.

4,4 (5- and/or 6 substituted-Z-norbornylidene)diphenols can be preparedaccording to the following schematic series of reactions:

r+ 3) itt H l H+ R R 2 2 \l/ For R and R see below, R is previouslydefined.

The first step of the reaction consists of a Diels-Alder reactionbetween a substituted ethylene and cyclopentadiene. This may beaccomplished by heating dicyclopentadiene with a substituted ethylene at200 C. in an autoclave for several hours. The reaction betweencyclopentadiene and styrene is described in Ber., 71, 384 (1938). Thebicycloheptene (VI) is then hydrated to give the norcamphanol (VII),which is oxidized to the ketone (VIII) with chromic acid or nitric acid.Condensation of a phenol with the substituted norcamphor (VIII) yieldsthe bisphenol (IX) (see Example 1).

Examples of substituted ethylenes which can be employed in this processinclude propylene, Z-butene, styrene, stilbene, p-chloro-styrene, andother homologous hydrocarbons and chlorinated hydrocarbons containingfrom 3 to 20 carbon atoms and from none to 6 chlorine atoms.

By employing 2-butene in this synthesis4,4-(5,6-dimethyl-Z-norbornylidene)diphenol Was prepared. When styrenewas used, the product was predominantly 4,4-(5-phenyl-2-norbornylidene)diphenol which was probably 9 in admixturewith its isomer with the phenyl radical in the 6-position. In a similarmanner, from stilbene was obtained4,4-(5,6-diphenyl-Z-norbornylidene)diphenol.

Example 4 4,4'-(2 norbornylmethylene) diphenols-One systhesis of thesebisphenols is as follows:

R=Hydrogen or one or several halogen atoms or alkyl groups (methyl,ethyl, propyl, or butyl) or aryl groups R"=Hydrogen, halogen, aryl, oralkyl (methyl, ethyl,

propyl, or butyl) R=Hydrogen or alkyl (methyl, ethyl, propyl, or butyl).3

All alkyl substituents may be branched (isopropyl, isobutyl, etc.).

There are two possible stereoisomers (endo and exo) of the bisphenolwhen R and R are hydrogen. When R and R are substituted, cis and transisomers of the endo and exo structures are possible.

The most convenient method of preparing the Diels- Alder adducts (X) isby heating dicyclopentadiene and o e-unsaturated aldehydes in anautoclave at 200 C. for about 1 hr. It is also convenient then tohydrogenate the double bond before removal of the product from theautoclave. Satisfactory hydrogenation conditions consist of roomtemperature and hydrogen at 500 p.s.i. (5 percent palladium on aluminacatalyst). Literature procedures for the preparation of some of thealdehydes are Ann, 460, 119 (1928) and Ann., 470, 67, 92 (1929). Thebisphenols were prepared as described in Example 1.

4,4 (2 norbornylmethylene)diphenol '(XI'I, R=H, 'R'=H, and R"=H) meltedat 207-208 C.

4,4 (3 methyl 2 norbornylmethylene)diphenol (XII, R=H, R"=CH R=H)consisted of an isomer (XII, R=H, R'=C H melted at 195-198 C.

4,4 (3 phenyl 2 norbornylmethylene)diphenol mixture and melted at222-224" C.

4,4 (2 norbornylmethylene)bis[2,6-dichlorophenol] (X11, R=H, R-=H,R"=Cl) prepared as described in Example 2, melted at 166-168 C., andgave the correct analysis for 4 chlorine atoms per molecule.

4,4 (3 methyl 2-norbornylmethylene)bis[2,6-dichlorophenol] (XII, R=H, R=CH R=Cl) was similarly prepared. It melted at 155-160 C. A chlorineanalysis proved that this compound was the tetrachloro derivative.

4,4 (2 norbornylmethylene)bis[2,6-dibromophenol] (XII, R=H, R'=H, R= Br)was prepared by treating 0.5 mole of the bisphenol (XII, R=H, R=H, R"=H)in 500 ml. of methanol at room temperature with 2 moles of bromine. Itmelted at 130-133 C.

4,4 (5 and/or 6 substituted-Z-nonbornylmethylene) diphenols can beprepared from intermediate VI of Example 3 by hydroformylation to thealdehyde and then condensation to give the bisphenol:

RI! l 2 OH Rr- CO+H2 R1 n I CHO Bisphenol R2 R R R and R" are previouslydefined (Example 3). The hydroformylation reactions were carried out byconventional procedures, using dicobalt octacarbonyl catalyst. A similarprocedure is described in J. Am. Chem. Soc., 74, 2095 (1952). A detailedprocedure is given in Example 10. The bisphenols were prepared asdescribed in Example 1.

Example 5 4,4 (hexahydro 4,7 methanoindan-S-ylidene)diphenols.-Thesebisphenols may be prepared as follows:

/E W 11,0 W on H2 R J) r R J) (XIII) (XIV) OH [O] o at 0 R Q M HNO; H+

(XV) (XVI) (XVII) In the above synthesis dicyclopentadiene is thestarting material when R=H, but substituted bisphenols may be obtainedfrom substituted dicyclopentadienes when R consists of one or morehalogen atoms or aryl groups or alkyl gorups (1 to 4 carbon atoms) inany or all of the polycyclic rings. R may be hydrogen or alkyl (1 to 4carbon atoms). Chlorine and bromine groups may be introduced on thepolycyclic rings by treating XIV, XV, or XVI with chlorine or bromine inthe presence of ultraviolet light.

Hydration of dicyclopentadiene with 25 percent sulfuric acid by theprocedure of Bruson and R-iener, I. Am. Chem, Soc., 67, 726 (1945), gave3a,4,5,6,7,7a-hexahydro-4,7-methanoindan-6-ol (XIV, R=H). The correctstructure for this compound was described by Bartlett and Schneider, J.Am. Chem. Soc., 68, 6 (1946). They pointed out that the five-memberedring in XIV was in the exo-position because a Wagner-Meerweinrearrangement took place during the hydration reaction. Hydrogenation ofXIV (R=H) gave hexahydr0-4,7-methonoindan- 5-01 (R=H). Because thisproduct is a solid, it was preferable to carry out the hydrogenation ina solvent. Hexane was used since, after removal of the catalyst, thesolution could be used directly in the next reaction (oxidation) withoutfurther purification. The saturated carbinol 1 1 in refluxing hexane wasoxidized to hexahydro-4,7-methanoindan-S-one (XVI, R H) withconcentrated nitric acid.

4,4 (hexahydro 4,7 methanoindan-S-ylidene)diphenol (XVII, R=H, R"=H),obtained as described in Example I, was solvated with one mole of waterwhen recrystallized from aqueous ethyl alcohol or aqueous acetic acid.It melted at 221-223 C. after losing its water of hydration.

4,4 (hexahydro 4,7 methanoindan-S-ylidene)di-ocresol (XVII, R=H and CHobtained from XVI and o-cresol, melted at 2082l0 C.

4,4 (hexahydro 4,7 methanoindan-S-ylidene)bis [2,6 dichlorophenol](XVII, R=Cl) was prepared by chlorination of XVII (R"=H) as described inExample 2. After purification by the disodium salt method of Example 2,it melted at 100 C. and gave the correct analysis for 4 chlorine atomsper molecule.

4,4 (hexahydro 4,7 methanoindan-S-ylidene)bis [2,6 dibromophenol] (XVII,R=Br) was prepared by treating one mole of the bisphenol suspended in1200 ml. of methanol at room temperature with 4 moles of bromine. Itmelted at 116-118 C. and gave the correct analysis for 4 bromine atomsper molecule.

Example 6 4,4 (dodecahydro 4,9,5,8 dimethano-l-cyclopenta(b)naphthalen 6ylidene)diphenols.-These hisphenols may be prepared as follows:

4W... OH H. et/ ut/0 R may be hydrogen or one or more halogen atoms oraryl groups or alkyl groups (1 to 4 carbon atoms) in any or all of thepolycyclic rings. R" is previously defined.

Hydration of tricyclopentadiene (XVIII, R=H) is described in J. Am.Chem. Soc., 67, 728 (1945), but a higher yield of XIX is obtained by themethod in I. Am. Chem. Soc., 69, 1827 (1947). The remainder of the syn-1 2 thesis may be carried out by the same procedures used in preparingXVII in Example 5. When R and R" were H the bisphenol melted at 210-215C.

Example 7 4,4 (decahydro 1,4:5,8 dimethanonaphth-Z-ylidene) diphenols.-The synthesis of exo-endo isomers of this class of bisphenols is asfollows:

I OCOCHz R t! \l/ (XXIII) (XXIV) (XXV) (XXVI) (XXVII) The synthesis ofthe ketone (XXVI) is described in Ann., 543, 20-21 (1940). The exo-endoring structure is assumed to be the same as that of the carbinol (XXV),which was proved by Soloway, J. Am. Chem. Soc., 74, 1027 (1952). Example1 gives a general procedure for preparing the bisphenols. Substitutedbisphenols may be obtained by starting the synthesis with a substitutedcyclopentadiene in which R is one or more halogen atoms, aryl groups, oralkyl groups. Intermediates XXIH, XXIV, XXV, and XXVI also may behalogenated by treating with bromine or chlorine in the presence ofultraviolet light.

4,4-(decahyd'ro-1,4-exo 5,8 -endo-dimethanonaphth- 2-ylidene)diphenol(XXVII, R and R ='H) was solvated with water when recrystallized fromaqueous ethyl alcohol. The bisphenol melted at 244-245 C. after losingits water of hydration.

4,4-(decahydro 1,4 exo-S,8-endo-dimethanonaphth- 2-ylidene)di-o-cresol(XXVII, R"=H and CH3) obtained from XXVI (R=H) and o-cresol, melted at212 214 C.

4,4'-(decahydro-1,4-exo 5,8 endo-dimethanonaphth-2-ylidene)bis[2,6-dichlorophenol] (XXVII, R-=Cl), prepared from XXVII (Rand R=H) and chlorine as described in Example 2, gave the correctanalysis for 4 chlorine atoms per molecule.

The synthesis of exo-exo isomers of this class of bisphenols is asfollows:

l l H+ I OH R R \ll/ 1120 i (XXVIII) (XXIX) (XXX) Example 84,4-(decahydro 1,4:5,8 dimethanonaphth-2-ylmethylene) diphenols.--Thesynthesis of these bisphenols is as follows:

R, R, and R" are the same as in XII.

If R' is H, 8 stereoisorners are possible. More are possible when R isnot H.

Aldehyde XXXII (R and R"=H) was prepared by a procedure similar to thatgiven in Ber., 71, 2413 (1938). The product, which contained sometricyclopentadiene (gas chromatogram), was reduced to the saturatedaldehyde at room temperature with hydrogen (500 p.s.i.) and 5 percentpalladium on alumina catalyst. It distilled at 112 C./2 mm.

4,4'-(decahyd'ro-l,4:5,8-dimethanonaphth 2 ylmethylene)dipheno1 (XXXIV,R=H, R"=H, R"=H), preparedby the method of Example 1, crystallized fromaqueous ethyl alcohol as a hydrate melting at 218-219 C. after loss ofits water.

4,4-(decahydro 1,4:5,8dimethanonaphth-Z-ylmethylene)bis[2,6-dichlorophenol] (XXXIV, R"=Cl),prepared by chlorination of the above bisphenol by the method of Example2, gave the correct analysis for 4 chlorine atoms per molecule.

Example 9 4,4 (hexahydro-4,7-methanoindan-5-ylmethy1ene)diphenols.Thesebisphenols may be prepared as follows:

(XXXV) RI! I CH0 1 R I RI! (XXXVI) llall R \.J R 2 (XXXVII) R and R" arepreviously defined.

1,Z-dihydrodicyclopentadiene (XXXV, R=H) was prepared by the Diels-Alderreaction between cyclopentene and dicyclopentadiene (which cracked tocyclopentadiene) at 198 C. This compound,endo-1,2-dihydrodicyclopentadiene, is described in J. Am. Chem. Soc.,82, 2361 (1960). This paper also describes the preparation of the exoderivative, which after the 0x0 reaction, can be used to give adifierent bisphenol isomer. As indicated, XXXVI (R=H) was prepared byhydroformylation. It boiled at 106-110 C./ 3 mm. The procedure wassimilar to that in US. Pat. 2,850,536, which describes thehydroformylation of dicyclopentadiene. Another similar hydroformylationprocedure is described in detail in the next example.

4,4 (hexahydro-4,7-methanoindan-5-ylmethylene)diphenol (XXXVII, R andR"=H), prepared by the method of Example 1, melted at 212-2l4 C. afterrecrystallization from acetic acid.

4,4 (hexahydro 4,7-methanoindan-S-ylrnethylene)-bis-[2,6-dichlorophenol] (XXXVII, R"=Cl), prepared by the method ofExample 2, gave the correct analysis for 4 chlorine atoms per molecule.

Example 10 4,4'- (hexahydro-4,7-methanoindan-2 (or 3 -ylmethylenediphenols.-These bisphenols may be prepared as (XXXIX) R and R" arepreviously defined.

When R=H the starting material is dicyclopentadiene. The active doublebond of dicyclopentadiene was hydrogenated to yield XXXVIII, and thisproduct was hydroformylated (oxo reaction) to yield aldehyde XXXIX.Specific procedures follow:

To a stirred mixture (magnetic stirrer) containing 264 g. (2.0 moles) ofdistilled dicyclopentadiene and 5 g. of 5 percent palladium or aluminain 300 ml. of ethanol was added hydrogen (45 p.s.i.) at room temperatureuntil two moles was taken up. The product, dihydrodicyclopentadiene, wasfiltered from the catalyst and distilled, B.P. 178-179" C. An autoclavewas charged with 156 grams of dihydrodicyclopentadiene in 500 ml. ofbenzene, and 3 g. of dicobalt octacarbonyl was added. After theautoclave was purged with nitrogen, hydrogen (800 p.s.i.) and then 1:1hydrogen-carbon monoxide (2000 p.s.i.) were pressed in. The mixture washeated to 150 C., and the pressure was held at 3000 p.s.i. with 1:1hydrogencarbon monoxide. After two hours, the mixture was cooled,filtered, and flash-distilled. When redistilled, the product,hexahydro-4,7-methanoindan-2(or 3)-carboxaldehyde, boiled at 107-113C./4 mm. n 1.5082.

4,4 (hexahydro-4,7-methanoindan-2(or 3)-ylmethylene) diphenol (XL, R andR"=H), prepared by the method of Example 1 and recrystallized fromaqueous acetic acid, melted at 220230 C. It consisted of an isomermixture.

4,4 (hexahydro-4,7-methanoindan-2(or 3)-ylmethyl ene)-bis[2,6-dichloropheuol] (XL, R"=C1), prepared by the method of Example 2,gave the correct analysis for 4 chlorine atoms per molecule.

Example 11 4,4' (hexahydro 4,7 methanoindan 1-ylidene)diphenols.Thesebisphenols may be prepared as follows:

2 be r R (XLI) (XLII) R and R" are previously defined.

When R is H the preparation of the ketone is given in Monatshefte 85,154 (1954); there are two possible stereoisomers having endo and exostructures, and if R is not hydrogen then isomers having cis and transstructures exist. This observation obviously also applies to otherexamples in this specification. When R and R"=H the bisphenol, preparedby the method of Example 1, melted at 213-215 C.

Example 12 4,4 (octahydro-4,7-methanoisobenzofuran-6-ylidene)diphenols.-The synthesis of the bisphenols is as follows:

$ CHZOH pTsCl R Q o R (XLIII) (XLIV) R HOAc K011 u) rs R or (XLV) (XLVI)0 R" R R:E. I

o 0 11+ (XLVII) (XLVIII) -OR {-11 W R" 2 (XLIX) R and R" are previouslydefined.

The synthesis of the endo and exo isomers of ketone XLVIII when R=H isdescribed by Culbertson Seward, and Wilder in I. Am. Chem. Soc., 82,2541-7 (1960). The starting material (XLIII) is the maleic anhydrideadduct of cyclopentadiene. It is obtained as the endo isomer. It can berearranged thermally, as described in the paper, to give the exo isomer,which is used to synthesize the exo bisphenol. (The endo bisphenol, ofcourse, is obtained from the endo Diels-Alder adduct.)

4,4 (octahydro-4,7-methanoisobenzofuran-6-ylidene) diphenol (XLIX, R andR"=H), prepared from the endo ketone (XLVIII) by the method of Example1, melted at 2l5-218 C.

4,4 (octahydro-4,7-methanoisobenzofuran-6-ylidene)bis-[2,6-dichlorophenol] (XLIX, R"=Cl) was prepared from the abovebisphenol by the method of Example 2. It was purified by recrystallizingits disodium salt from a mixture of ethyl alcohol and acetone and thenregenerating the bisphenol with acetic acid.

Example 13 f NaNO A H LIV R and R" are previously defined.

The unsaturated nitrile (L) is obtained by the Diels- Alder reactionbetween cyclopentadiene or a substituted cyclopentadiene andacrylonitrile. Hydrogenation in the presence of ammonia yields thesaturated amine (LI). The preparations of these two compounds when R=Hare described in Ber. 88, 152 (1955). When the amine is treated withnitrous acid, the ring expands and bicyclo [3.2.1]octan-2-ol (LII, R=H)is obtained. Oxidation with potassium dichromate converts it to theketone (LIII). The preparations of the carbinol and ketone are describedin Ber. 71, 2407 (1938).

4,4-(bicyclo[3.2.1]oct-2-ylidene)diphenol (LIV, R and R"=H), prepared bythe method of Example 1, melted at 204-207 C.

4,4 (bicyclo[3.2.1]oct-2-ylidene)bis[2,6 dichlorophenol] (LIV, R"=C) wasprepared from the above bisphenol by the method of Example 2.

Example 14 4,4 (bicyclo[3.2.2.]non-2-ylidene)diphenols.-These bisphenolsmay be prepared as follows:

on o

r mo, 2

R and R" are previously defined.

The unsaturated nitrile (LV) is obtained by the Diels- Alder reactionbetween cyclohexadiene or a substituted cyclohexadiene andacrylonitrile. Hydrogenation in the presence of ammonia yields thesaturated amine (LVI). When this compound is treated with nitrous acid,the ring expands and a bicyclo[3.2.2.]nonan-Z-ol (LVII) is obtained.When R=H these preparations are described in Ber. 88, 153 (1955).Oxidation with potassium dichromate converts the carbinol to ketone(LVIII).

4,4-(bicyclo[3.2.2.]non-2-ylidene)diphenol (LIX, R and R-:H), preparedby the method of Example 1, melted at 218220 C.

4,4 (bicyclo[3.2.2.]non-2-ylidene)bis[2,6 dichlorophenol] (LIX, R"=Cl)was prepared from the above bis- LII .18 phenol and chlorine by themethod of Example 2. A chlorine analysis proved that this compound wasthe tetrachloro derivative.

OH o

Example 15 4,4 (bicyclo[2.2.2]oct-2-ylmethylene)diphenols. Thesebisphenols may be prepared as follows:

DC an I cu at) am n 2 R, R, and R" are the same as in Example 4.

The Diels-Alder adduct LX is obtained by condensing cyclohexadiene or asubstituted cyclohexadiene with an u,B-unsaturated aldehyde. Catalytichydrogenation of the double bond gives the saturated aldehyde (LXI). Thepreparation of these two compounds when R equals H is described in I.Am. Chem. Soc. 74, 3001 (1952).

4,4 (bicyclo[2.2.2]oct-2-ylmethylene)diphenol (LXII, R=H, R=H), preparedby the procedure of Example 1, melted 224226 C.

4,4 (bicyclo[2.2.2]oct 2 ylmethylene)bis[2,6 dichlorophenol] (LXII,R"=Cl) was prepared by chlorination of the above bisphenol by theprocedure of Example 2.

Example 16 4,4 (spiro[cyclopropane-1,7'-norborn 2'yl]methylene)diphenols.-'I'hese bisphenols may be prepared as follows:

R can one 2 0H 1, new cacao R: Q R 7%] @Y W R i mm my R and 'R" arepreviously defined.

Preparation of spiro(cyclopropanecyclopentadiene) (LXIII, R=H) isdescribed by Alder et al. in Ber. 93, 1892 (1960). A Diels-Alderreaction between this compound and an c p-unsaturated aldehyde yieldsthe adduct (LXIV). The saturated cyclic aldehyde (LXV) is obtained bycatalytic reduction of the double bond. Bisphenols are obtained bystirring an aldehyde with a phenol in an acidic medium. Detailedprocedures follow:

Spiro[cyclopropanecyclopentadiene] was heated on a steam bath with anequimolar amount of acrolein for 12 hours. Distillation yielded theDiels-Alder adduct, B.P. 80-84 C./ 16 mm. The double bond was reduced byplacing 200 g. of the adduct in an autoclave with g. of 5 percentpalladium on alumina and hydrogenating at room temperature and 500p.s.i. The catalyst was removed by filtration, and the saturatedaldehyde (LXV, R=H) was used to prepare the bisphenol by the method ofExample 1. It melted at 212215 C.

Example 17 4,4 (tricyclo[2.2.1.0 ]heptan 3 ylidene)diphenols.-Thesebisphenols may be prepared as follows:

R and R are previously defined.

When a norbornene (LXVII) is treated with N-bromosuccinimide, arearrangement takes place and the 3-bro monortricyclene (LXVIlI) isobtained. The bromo group is hydrolyzed to form the hydroxy compound(LXIX), which is then oxidized to the ketone (LXX). The ketone is thentreated with a phenol by the method of Example 1 to form the bisphenol.When R and R"='H, the bisphenol melted at 211212 C. afterrecrystallization from ethylene dichloride containing a small amount ofethyl alcohol.

The preparation of the ketone (LXX) from 2-norbornene when R equals H isdescribed by Roberts and coworkers (I. Am. Chem. Soc., 72, 3123 (1950)).The article also gives the structure of the ketone (p. 3117) of whichLXX is a planar representation. It is referred to as nortricyclanone byRoberts and tricyclo[2.2.1 ]heptan-3-one by Chemical Abstracts. WhenR=H, a simpler synthesis begins with norbornadiene (LXXII):

l HCOOH OOCH HOH w \l/ (LXXII) N-brornoaucclnlmide (LXXIII) (LXIX) (R=H)The preparation of the above carbinol by this method is described bySchmerling and co-workers [1. Am. Chem. Soc., 78, 2821 (1956)]. Duringthe addition of formic acid to norbornadiene, rearrangement occurs andthe formate (LXXIII) is obtained. This may then be hydrolyzed to thecarbinol, which is oxidized to the ketone (LXX, R=H) as before.

4,4 (tricyclo[2.2.l.0 ]heptan 3 ylidene)bis[2,6- dichlorophenol] wasprepared by chlorination of the above bisphenol by the procedure ofExample 2.

BISPHENOL POLYCARBONATES Polycarbonates from bisphenols may be preparedby adding phosgene and/or a bischloroformate of a diol, to a cooled,stirred aqueous mixture containing sodium hydroxide, the bisphenol, acatalyst, and methylene chloride. On further stirring the polymer buildsup in the methylene chloride phase.

20 A bisphenol (residue shown by OB-O) and phosgene give recurringstructural units in the polymer of:

A bisphenol and a dischloroformate of a diol (residue shown by giverecurring structural units of:

The diol from which the bischloroformate is prepared may be aromatic,aliphatic, or alicyclic, and may be primary, secondary, or tertiary. Thecarbon chain of aliphatic diols may be straight, or branched and maycontain from 2 to 20 carbon atoms. Examples of diols are ethyleneglycol; 1,6-hexanediol; 1,4-hexanediol; 1,4-cyclohexanedimethanol;p-xylylenediol; 2,5-norbornanediol; trans-1,4-cyclohexanediol; 2,5dimethyl-2,5-hexanediol; hydroquinone; and 4,4-isopropylidenediphenol.Also any of the following groups may be present in the molecule (R=alkylor aryl): R C, o -OCH CH O, S, --SO-, SO SO NR, -NR-,

CO, COO, CF --NRNR, CH=CH, --C:C, phenylene, cyclohexylene, etc.

Bischloroformates of aliphatic and alicyclic diols may be prepared byadding an excess of phosgene to the diol suspended in ethylenedichloride. If the diol reacts very slowly, some dry dixoane is alsoadded to increase its solubility in the medium. After all of the diolhas been dissolved, dry air is passed in until all of the hydrogenchloride and excess phosgene has been swept out. The bischloroformatesolution may then be used as needed in the polymerization reactions.

Bischloroformates of aromatic diols, including bisphenols, may beprepared by simultaneously adding the diol (dissolved in dioxane) anddimethylaniline to a stirred solution of phosgene in toluene. A similarprocedure is described in British Patent 613,280.

When a bischloroformate is added to the reaction mixture, the molaramount of the bisphenol preferably should be equal or in slight excess(5 mole percent). When phosgene and a bischloroformate are both added,or the phosgene alone is used, the phosgene preferably should be 5 to 10mole percent in excess of its equivalent bisphenol in the reactionmixture.

A quaternary ammonium salt or hydroxide increases the rate ofpolymerization. This may also be accomplished with certain tertiaryamines, such as tri-n-butyl amine, which is preferred.

The optimum temperature range is 1525 C. At lower temperatures a longerreaction time is required. At higher temperatures hydrolysis tends tolower the inherent viscosity of the polymer product.

Depending upon the catalyst used, the normal reaction time to obtain amaximum molecular weight product will be from 10 minutes to 2 hours.Reaction rate is slower if impure reactants are used or if catalyst isnot used. Longer reaction time permits hydrolysis which tends to lowerthe molecular weight. At the end of the reaction time the alkali presentmust be neutralized with acetic, hydrochloric, or other acid.

After the reaction is completed, the polymer layer is diluted 'by addingmethylene chloride and then is washed thoroughly with Water. The polymercan be precipitated by slowly pouring the methylene chloride phase intomethanol, hexane, or other non-solvent.

In addition to the interfacial process, just described, for preparingthe polycarbonates of this invention, these polymers may also beprepared by adding phosgene and/ or a diol bischloroformate to a stirredmixture containing the bisphenol and a tertiary amine, such as pyridineor triethylamine. A portion of the tertiary amine may be replaced with asolvent for the polymers, such as methylene chloride. In contrast to theinterfacial process, in this process it is not necessary to addnonaromatic diols in the form of their bi-schloroformates the diolsthemselves may be added. Copolycarbonates are then obtained whenphosgene is added to the bisphenol/diol mixture in the tertiary amine.

These polycarbonates also may be prepared by the ester interchangeprocess, that is, by heating the bisphenol, a diaryl carbonate, and asuitable catalyst under reduced pressure. Satisfactory diaryl carbonatesinclude diphenyl carbonate, ditolyl carbonate, dixylyl carbonate, anddinitrophenyl carbonate. Catalysts include the oxides, hydrides, andhydroxides of alkali metals and alkaline earth metals and also the freealkali and alkaline earth metals. Other suitable catalysts include butyllithium, phenyl lithium, zinc oxide, lead oxide, dibutyltin oxide, andsodium aluminate. The usual method is followed of heating the reactantsunder reduced pressure to remove the phenolic compound as thecondensation proceeds. Required temperatures are 250-350 C. It ispreferred to build up final molecular weight by the solid-phase processin which the granulated polymer is heated under reduced pressure(preferably below 1 mm. of mercury) at a temperature somewhat below itsmelting point. Experimental procedures are similar to those given underthe section entitled Preparation of Bisphenol Polyesters wherein diarylesters of dicarboxylic acids are used instead of diaryl carbonates.

The polycarbonates of this invention include copolymers.Copolycarbonates are prepared by condensing a mixture of more than onebisphenol with phosgene or a (1101 bischloroformate or a diarylcarbonate, or of a bisphenol with a mixture of more than one diolbischloroformate. Block copolycarbonates are prepared by condensing amixture of low-molecular weight homopolycarbonates with phosgene. Mixedcopolymers are prepared by condensing. a bisphenol with abischloroformate of a polymeric diol (e.g. polyethylene oxidebischloroformate).

Bisphenols which may be used with the bisphenols of this invention forpreparing copolycarbonates include 4,4- isopropylidenediphenol (alsoknown as bisphenol A), 4,4- isopropylidenebis[2,6-dichlorophenol], 4,4isopropylidenebis[2,6-dibromophenol], cyclohexylidenediphenol,cyclohexylmethylenediphenol, 4,4'-sulfonyldiphenol, 4,4- oxydiphenol,4,4'-dihydroxyphenyl, 4,4'-rnethylenediphenol, hydroquinone, resorcinol,1,4-naphthalenediol, 2,5- naphthalenediol, and other bisphenols listedin US. Pat. 3,030,335.

A general procedure for preparing the new polycarbonates from polycyclicbisphenols and phosgene by the interfacial method is given in Example18. This method was used for most of the polymers. These polymers canalso easily be prepared by the tertiary amine method, which is describedin Example 19. This method is particularly valuable for preparingpolymers from halogenated bisphenols. Example 20 describes thepreparation of polycarbonates from bisphenols and diolbischloroformates. Examples 21 describes a preparation of blockcopolycarbonates from two bisphenols and phosgene. Example 22 describesthe preparation of block copolycarbonates from bisphenols, phosgene, andpolymeric diol bischloroformates.

Example 18 General procedure for preparing polycarbonates formbisphenols and phosgene (interfacial method) .In a wellventilated hood a500 ml., three-necked flask is fitted with a stirrer, thermometer, andglass inlet tube which extends beneath the surface of the reactionmixture. A flowmeter containing a glass ball float (to indicate the rateof phosgene addition) and a trap are placed between the inlet tube andthe lecture bottle of phosgene. Also attached to the system to relieveany excess pressure is a tube leading under about one inch of mercury ina side-arm test tube. The phosgene lecture bottle, attached to thesystem through a piece of neoprene tubing, is continuously weighed on abalance to follow the addition. To determine the exact amount ofphosgene added, the lecture bottle, disconnected from the system, isWeighed before and after the addition. Glass tubing is used as much aspossible since rubber tubing deteriorates in the presence of phosgene.During the addition of phosgene the reaction mixture is cooled with acold-water bath to keep the temperature below 25 C. (usually 15-20 C.).The bath is then removed while the polymer is building up.

To the flask are added 12 g. of sodium hydroxide dissolved in 200 ml. ofwater, 0.10 mole of the bisphenol, ml. of methylene chloride, and 4drops (0.06 g.) of tributylamine. [Benzyltriethylammonium chloridecatalyst (1.0 g./ 0.1 mole of bisphenol) was used in preparing some ofthe polymers, but tributylamine is more effective and gives a fasterpolymerization] If the mixture becomes too thick and mushy due to theformation of an insoluble bisphenol sodium salt, more water is added.While this mixture is stirred and cooled in a cold-water bath whichholds the reaction temperature at about 20 C., phosgene is passed infrom the lecture bottle at a rate of about 1 g./ min. until the loss inweight of the bottle is 10.5-11.0 g. If some of the bisphenol or itssalt has not gone into solution by this time, more phosgene and aqueoussodium hydroxide (to keep the pH above 12) are added. Also, morephosgene is added if the aqueous layer becomes turbid on acidificationof a portion. Usually during the next 10-60 min. the methylene chloridelayer becomes very viscous. The mixture is then neutralized with aceticor hydrochloric acid and diluted with more methylene chloride. By thisprocedure a polycarbonate with an inherent viscosity (in chloroform) ofapproximately 1.0 is obtained. An appreciably higher inherent viscositycan be obtained by diluting the mixture With more methylene chloride andallowing the polymerization to proceed longer before neutralization.Lower inherent viscosities are obtained by neutralizing the mixturesooner.

After the neutralized reaction mixture is stirred for 1 hr., deionizedwater is passed in through a tube extending to the bottom of the flaskwhile stirring is continued. The water is allowed to overflow into thesink during this Washing period of several hours.

All of the polycarbonates can be precipitated, usually as white, fibrousproducts, by adding the methylene chloride layer to several volumes ofhexane or heptane with stirring. Many of the polymers can also beprecipitated in methanol, ethyl alcohol, isopropyl alcohol, or acetonein this manner. It is preferable that the methylene chloride layer notbe thick to prevent the polymer from separating first as a gummymaterial. The most convenient method of precipitation, which is noteflective with all of the polymers, is to add acetone slowly to themethylene chloride layer with stirring. The polycarbonate precipitatesas small particles. After the mixture is stirred for 15 to 30 min.,about two-thirds of the solvent is decanted, and an equal volume ofhexane or heptane is added with stirring to cause the polymer particlesto harden slightly. (The particles of some polymers coagulate into anelastic mass when the hydrocarbon is not added.) This mixture is stirredfor 30 min., and then the solvent is then completely decanted. Hexane orheptane is added and the mixture stirred for 30 min. to complete thehardening of the particles. The polymer is then collected and dried.

23 Example 19 General procedure for preparing polycarbonates frombisphenols and phosgene (tertiary amine methd).-A 500-ml, three-neckedflask is set up in the apparatus described in Example 18. To the flaskare added 300 ml. of methylene chloride, 50 ml. of dry pyridine and 0.10mole of the unhydrated bisphenol. While the mixture is stirred and thetemperature is held at 2530 C. by means of the cold-water bath, phosgeneis passed in at a rate of about 1 g./ min. After about one-half of thetheoretical amount of phosgene has been added, pyridine hydrochlorideprecipitates. When 9.6-9.8 g. of phosgene has been added, the additionrate is decreased to about 0.1 g./ min. The addition is stopped when themixture becomes very viscous. About 10.5 g. of phosgene is required: Themixture is then poured into a large volume of water. More methylenechloride is added to dilute the organic layer, and hydrochloric acid isadded until the pH of the stirred mixture is 1.5. The methylene chloridelayer is washed with water and the polymer precipitated as describedunder the interfacial method. The inherent viscosity of the polymer isabout 1.2-1.6 (depending upon the weight of bisphenol used initially).

Example 20 General procedure for preparing polycarbonates frombisphenols and diol bischloroformates-This procedure describes thepreparation of these polymers by the interfacial method. The polymerscan also 'be prepared by adding the biscoloroformate to an equimolaramount of the bisphenol dissolved in a teriary amine methylene chloridemixture.

A 500 ml., three-necked flask is set up in the apparatus described inExample 18. To the flask are added 0.20 mole of sodium hydroxidedissolved in 200 ml. of water, 0.10 mole of the bisphenol, 150 ml. ofmethylene chloride, and 4 drops (0.06 g.) of tributylamine. While thismixture is stirred and cooled in a water bath which holds the reactiontemperature at about 20 C., 0.095 mole of the diol bischloroformatedissolved in 100 ml. of ethylene dichloride is added. Usually during thenext -60 min. the methylene chloride layer becomes very viscous. Themixture is then neutralized with acetic or hydrochloric acid and treatedas in Example 18 to wash and isolate the polymer. Higher polymermolecular weights are obtained by diluting the viscous methylenechloride layer with more methylene chloride and allowing polymerizationto proceed further.

Example 21 Procedure for preparing block copolycarbonates from twobisphenols and phosgene.-Block copolycarbonates can be prepared bymanufacturing in separate reaction vessels low molecular polycarbonateshaving molecular weights corresponding to inherent viscosities measuresin chloroform of from about 0.05 to about 0.4. Such molecular weights asa rough estimate will be less than about 10,000. The preparation of thelow molecular weight polycarbonates is substantially the same as thatdescribed hereinabove for the preparation of the high molecular weightpolycarbonates except that the polymerization is not allowed to proceedbeyond a point where the inherent viscosity surpasses about 0.4. Thiscan be readily determined by those skilled in the art using normaltechniques for approximating the I.V. values. It is advantageous toprepare the two separate blocks in the form of their low molecularweight polycarbonates at the same time so that when they have reachedthe desired molecular weights the two reaction mixtures can be mixedtogether, additional phosgene added and the reaction continued until thedesired inherent viscosity is achieved for the final polycarbonatehaving the molecular weight being sought. A typical procedure follows:

Three grams of phosgene was added to a mixture con- 24 taining 4 gramsof sodium hydroxide, 50 ml. of water, 8 grams of bisphenol A (0.035)mole), 2 drops of tributylamine, and 30 ml. of methylenechloride. Themixture was stirred for two minutes. This product was a low molecularweight polycarbonate suitable for the formation of a blockcopolycarbonate.

In a separate reaction vessel simultaneously with the precedingpreparation, there was added 1.7 grams of phosgene to a mixture of 2.0grams of sodium hydroxide, 60 ml. of water, 6.3 grams of4,4'-(2-norbornylidene)bis [2,6-dichlorophenol], 1 drop oftributylamine, and 20 ml. of methylene chloride which was then stirredfor 10 minutes. This low molecular weight polycarbonate had an inherentviscosity within the specified range and was suitable for thepreparation of a block copolycarbonate.

The two low molecular weight polycarbonates described in the precedingtwo paragraphs were mixed together immediately following the timeperiods of reaction previously indicated, 1.0 gram of phosgene was addedand the mixture was stirred continuously until the methylene chloridelayer was very thick. It was then diluted with more methylene chloride;neutralized with acetic acid, and washed with water. The resulting blockcopolycarbonate was precipitated in ethanol or some other suitablenonsolvent.

Example 22 Procedure for preparing block copolycarbonates frombisphenols, phosgene, and polymeric diol bischloroformatesThis procedureconsists simply of a modification of Example 18. After the addition of8.0 g. of phosgene to the bisphenol reaction mixture described inExample 18, the polymeric diol bischloroformate is added, followed bysuflicient phosgene to buildup the polymer to a high molecular weight.The polymer is then washed and isolated as in Example 18.

PROPERTIES OF POLYCARBONATE FILMS Some of the properties obtained onfilms of the polycyclic bisphenol polycarbonates are listed in Table 1.All films were cast from methylene chloride by conventional techniques.The films, l-3 mils thick, were air-dried and then heated in an oven at110 C. for 1-2 hours to ensure the removal of all solvent. All filmswere tough, and they were completely transparent and colorless.

The inherent viscosities (I.V.) of the polymers were measured inchloroform. The heat-distortion temperatures of the films (2 percentdeflection with 50-p.s.i. load) were measured in a forced convectionoven (ASTM D1637- 61). The second-order transition temperature was takenas the temperature at which the film distorted (shrank) percent at aload of 5 p.s.i. when heated in the above oven. Tensile properties weremeasured in accordance with ASTM D88261T Method A.

The tensile modulus values of the films are given in the table, but thetensile strength values (yield and break) are not listed because theyall fall in a comparatively narrow range (9,00016,000 p.s.i. and usually10,000- 12,000 p.s.i.) the elongations also are not listed because theydepend upon the film casting conditions. The elongations were usually3-30 percent, but films have been cast with elongations up to percent.The highest elongations were obtained on films with inherent viscositiesof 2.0 and higher, the lowest elongations (38 percent) were obtained onfilms from the halogenated bisphenol polymers. The elongations andtensile strengths were increased by stretching the films at temperaturessomewhat below their second-order transition temperatures.

Contrary to what might be expected of soluble, noncrystalline polymerscontaining bulky side groups attached to the main polymer chain, thesepolymers softened at very high temperaturesabove 300 C. in most cases.Since many of the polymers softened at such high temperatures that theydecomposed, the values had little melting. The second-order transisionand heat-distortion temperatures are more accurate measures of the high-25 26 temperature usefulness of the polymers. Softening temtric constantover a wide frequency and temperature range peratures are listed inTable 1 when second-order transi- (ASTM Dl49-6l and Dl50-59T). tion orheat-distortion temperatures were not determined. Films of allhomopolycarbonates prepared from his- The diol bischloroformates listedin Table 1 are abphenols containing 4 halogen atoms were nonburningacbreviated as follows: cording to ASTM D568-61.

1 clohexanedimethan o1 bischloroformate cH CH 5 The films had excellentthermal and oxidative stability: zzdimethybl,3 propanediolbisch1oroformate DM clf they remained tough while being heated in air at200 C.

Ethylene glycol bischloroformateEG Clf for 4 days 2,5-norbornanediolbisch1orof0rmate-ND Clf Compared to most other polymers, with increasing10 wt. percent polyethyleneoxide (IILW. 1500) bischolotemperature thereis only a relatively slow decrease of f t -41E Clf (10) 10 tensilestrength and tensile modulus of these polycyclic 27 wt. percentpolypropyleneoxide (m.wt. 200) bischlorobisphenol polycarbonates. Thisis illustrated for a few of formatePP Clf (27) the polymers in Table 2.Even at 200 C. the tensile 2d Order Heat Dis- Trans. tortion Modulus,Softening Bisphenol Halide I.V. Temp., C. Temp.,C. 10 p.s.i. Temp., C.

4,4-g-norbornylidene) diphenol Do Do (Z-norbornylidene)di-o-cresol 4-4,4-(2-norbornylidene) bis[2,6-dimethylpheno1]4,4'-(2-norbornylidene)bis-[2-chlorophenol]4,4-(2-norbornylidene)bis-[2,6-dichlorophenol}4,4-(2-norbornylidene)bis'[2,6-dichloropheno1 and bisphenol Aprepolymers (Example 21). Gopolyrner from equimolar amounts of preceding2 bisphenols 0.7 4,4-(2-norbornylidene)bis-[2,6-dibromophenol] 0. 44,4'-(5,6-dimethyl-2-norbornylidene) diphenol. 1. 24,4-(5,fi-diphenyl-Z-norbornylidene)diphenol '0. 84,4-(2-norbornylmethylene)diphenol 1. 1 Do l. 1. 7 1. 0 0. 7 0. 8 0. 5

l. 1 0. 7 1. 5 1. 0 0. 7 2. 0 0. 6 O 0. 5 PE Clf(20), 00012.. 1. 1 Do0001?, PP C1f(27) 0.8 4,4-(hexahydro-4,7-rnethanoindan-5-y1dene)d1-o-cresol C001 1. 34,4-(hexahydro-4,7-methanoindan-dylidene)bis[2,6-dich1oropheno1] 1. 54,4-ShexahydroAJ-methauoindan-5-y1idene) bis[2,6-dibromophe- C0012 0. 4

n 4,4-(dodecahydro4,9,5,B-dimethano-l-eyelopenta(b)naphthalen-6- C00121.0

yhgeneydiphenol.

Do 2 4,4-(decahydro-l,4-ex0-5,8-endodimethauonaphth-Z-yhdene)- 8diphenol.

D0 EGClf--- 1.04,4(dec1ahydro-1,4-exo-5,8-endodimethanonaphth-Z-ylidene)di-o- C 0012 0.8

creso 4,4-(decahydr0-1,4exo-5,8-endodimethanonaphth-2-ylidene)bis[2,6- O0012 0. 6

dichloroph enol]. 4, g(dlecaliydro-1,4-exo-5,8-exodimethanonaphth-2-yhdene)- C0012 1. 0

1 eno 1 )0 ND Clf 1. 34,4-(decahydro1,4:5,8-dimethanonaphth-Z-ylmethylene)diphenol. C 0012 1.6 4,4-(decahydro-1,4: 5,8-dimethanonaphth-2-yhnethylene)bis[2,6- COCIz0. 7

dichlorophenol]. 4,4-(hexahydro-4,7-methanoindan-5-ylmethylene) diphenolC 0012 0. 8 4AghexfihydroAJ-methanoindan-5-ylmethylene)bis[2,6-diehloro-C 0 C12 0. 8

p eno 4,4-(hexahydro-4,7-methanoindan-2 or 3-ylmethy1ene) diphenol N Do4,4-(hexahydro-4,7-methanoindan-2 or 3-ylmethylene)bis[2,6- C

dichlorophenol].

4,4(hexahydro-4,7-methanoindan-l-ylidene) diphenol Do 4,4-(octahydro-4,7-meth auoisobenz oluran-6-ylidene) diphenol4,4-(octahydro-4,7-methanoisob enzoiuran-dylidene)b1s[2,6-

diehlorophenol] 4,4'-(bicyclo[3.2.1]oct-2-ylidene)-diphenol 4,4-(bicyclo[3.2. 1] oct-2-ylidene)-bis [2,6-dich1or0phen0l] 4,4 -(bicyclo[3.2.2] non-2-ylidene) -dlphenol 4,4-(bicyclo[2.2.2] Oct-2-ylimethylene)diphenol 4,4- bicyclo [2. 2 .2] oct-2-ylmethylene) bis [2 fi-dichlorophon n11 4,4- (3-methylbicyclo [2 2. 2] oct-2-ylmethylene) diph an 01 Thepolycarbonate films had excellent electrical properstrengths and moduliare appreciable. At the bottom of ties: high dielectric strength, highvolume resistivity, low 75 the table are the corresponding properties oftwo comdissipation factor, constant dissipation factor and dielecmercialpolymers.

Yield Strength, p.s.l.

Break Strength Modulus 10 psi.

Polycarbonate From- 100 0. 150 C. 200 0. 100 0. 150 0. 200 C. 100 C. 1500. 200 C.

4,4-(2-norbornylidene)diphenol. 4, 500 5, 2, 3 4,4-(2-norbornylidenc)bis [2,0-dichlorophenol] 0, 300 5, 500 4, 400 Not measured 1. 04,4-(2-norbornylmethylcne)-diphenol 3, 000 4, 000 3, 500 2. 2 4,4-(2norbornylmethylene) bis-[2,6-dichlorophenol]. 4, 800 4, 90 2, 54,4-(3-methyl-2-norbornylmethylene)diphenol 6, 500 4, 900 3, 600 6,8005, 700 3, 800 1. 8 4,4-(hexahydro-4,7-methanoindan-5-ylidene)diphcnol 8,500 5, 200 3, 800 7, 500 4, 500 2, 700 2. 0 4,4-is0propylidcnediphenol5, 500 2, 300 0 Not measured 0. 0 Poly(ethyleneterephthalate) polyester5, 100 1, 900 750 Not measured 0. 3

PROPERTIES OF POLYCARBONATE MOLDING PLASTICS phenol,4,4'-dihydroxydiphenyl, 4,4-methylenediphenol, hydroquinone, resorcinol,1,4-naphthalenediol, 2,5-naphthalenediol, and other bisphenols listed inU.S. Pat. 3,030,335.

The ester interchange between a bisphenol and the phenyl or cresyl esterof the dicarboxylic acid is catalyzed by the oxide, hydroxide, orhydride of an alkali metal or alkaline earth metal or by the free alkalior alkaline earth metal itself. Other suitable catalysts include zincoxide, lead oxide, dibutyltin oxide, sodium aluminate, butyl lithium,and phenyl lithium.

The usual method is followed of heating the reactants under vacuum toremove phenol or cresol as the condensation proceeds. It is preferred tobuild up final molecular TABLE 3.-PROPERTIES OF INJECTION-MOLDEDPOLYOARBONATES Amt. of Izod Impact Bisphenol Heat- Strength Ft.- TensileStrengtl1,p.s.l. Elong. at A Mole Distortion lb./ In. of Break,Polycarbonate Frompercent Temp., C. Notch At Yield At Break percent4,4-(2-norbornylidene)diphenoL 233 0. 8 11, 600 10, 300 544,4'-(2-110rbornylidene)bis[2,6-dichlorophenol] 70 199 0. 8 10, 800 9,500 29 4,4-(241mb0rnylidenc)bis[2,6 dibromophen0l] 86 179 10, 500 9, 30048 4,4-(Z-norbornylmethylene)diphenol 9 3 8004,4'-(3-methyl-z-norbornyhnethylene)diphenol 2 6 1. 3 10, 800 10, 200 304,4-(hexahydro-4,7-rncthanoindamS-ylidene)diphenol. 204 1. 2 11, 200 9,900 30 4,4-isopropylidenediphenol 153 16 8, 800 11, 400 95 180 0. 0 12,000 11, 000 60 Nylon 60 polyamide.

4,4-isopropylidenediphenol, added to give a copolymer.

Rockwell hardness values were very high, about R124. The electricalproperties were the same as those of the films (high dielectricstrength, high volume resistivity, low dissipation factor, and constantdissipation factor and dielectric constant over a wide frequency andtemperature range). In addition, the two copolymers from halogenatedbisphenols were nonbuming according to ASTM D635-56T. The otherpolycarbonates in Table 3 were self-extinguishing according to thistest.

BISPHENOL POLYESTERS The dicarboxylic acid polyesters of this inventionare prepared by condensing the novel polycyclic bisphenols withdicarboxylic acids by ester interchange reactions between the novelbisphenols and esters of aliphatic, cycloaliphatic, and aromaticdicarboxylic acids. Phenyl or cresyl esters of the dicarboxylic acidsare convenient to use. Suitable aliphatic dicarboxylic acids includeoxalic, dimethylmalonic, succinic, glutaric, adipic, pimelic, azelaic,sebacic, and Z-methyladipic. Suitable cycloaliphatic acids includecyclohexane-1,4-dicarboxylic acid, cyclohexane-1,3-dicarboxylic acid,cyclopentane-1,3-dicarboxylic acid, and 2,5-norbornane-dicarboxylicacid. Either cisor trans-forms of the acids may be used. Suitablearomatic dicarboxylic acids include terephthalic, iso phthalic,t-butylisophthalic, diphenic, 4,4'-sulfonyldibenzoic, 4,4'-oxydibenzoic,and 2,5-naphthalene-dicarboxylic. Other suitable acids are those foundin column 7 of U.S. Pat. 2,720,506. Mixtures containing two or moreacids, two or more bisphenols or an aliphatic or cycloaliphatic glycolwith the bisphenol may be used to give copolyesters.

Bisphenols which may be added with the polycyclic bisphenols to givecopolyesters include 4,4-isopropylidenediphenol (commonly known asbisphenol A), 4,4'-isopr0- pylidenebis[2,6 dichlorophenol], 4,4isopropylidenebis [2,6-dibromophenol], cyclohexylidenediphenol,cyclohexylmethylenediphenol, 4,4'-sulfonyldiphenol, 4,4-oxyldiweight bythe solid-phase process in which the granulated polymer is heated in avacuum at a temperature somewhat below the melting point. It isdifficult with the polyesters of this invention to build up molecularweight by melt polymerization due to the very high melt viscositiesinherent in the polymers.

Polycarboxylates may also be prepared from the dicarboxylic acidchlorides by heating a mixture of equivalent amounts of bisphenol andacid chloride at temperatures from -280" C. or higher, or they may bereacted in a basic solvent such as pyridine or in a 2-phase systemconsisting of aqueous alkali and organic solvent phases as described inJ. Poly. Sc., 40, 399 (1959).

Another process involves the ester interchange reaction of a monobasicaliphatic acid ester of the bisphenol with a dicarboxylic acid. Theester is heated with the acid to promote ester interchange withelimination of the monobasic acid. The final stage of the polymerizationis carried out under vacuum. A catalyst such as manganese will speed thereaction.

EXAMPLE 23 General procedure for prepdring polyesters from bisphenolsana diphenyl diesters.Nitrogen is added to displace the air from a flaskcontaining 0.030 mole of the bisphenol, 0.030 mole of the dicarboxylicacid diphenyl ester, 0.001 g. of calcium hydride, and either 0.0005 g.of lithium hydride or 0.01 g. of sodium aluminate. (If the bisphenol ischlorinated, it is preferable to add 0.01 g. of dibutyltin oxide for thecatalyst.) The mixture is melted down with stirring at 200 C. A vacuumof 30 mm. is applied, and phenol is distilled from the reaction mixturewhile it is heated to 280 C. The pressure is then reduced to about 0.5mm., and heating is continued at 280300 C. Usually during the next 10-60minutes the polymer attains a high melt viscosity. It is cooled undervacuum, treated with acetone to aid in hardening, and ground to pass a20-mesh screen. The molecular weight of the polymer is further increasedby heating at about 0.1 mm. while the temperature is raised during 1 hr.from 180 C. to a value somewhat below the polymer melting point.Temperatures of 315-350 C. are normally satisfactory. This finaltemperature is then held for another hour.

Some of the copolymers, such as those prepared from an appreciableamount of diphenyl azelate or diphenyl sebacate, melt below 300 C. Thesepolymers are built up to their final molecular weights in the melt.

PROPERTIES OF BISPHENOL POLYESTERS Some of the properties obtained onfilms of the polycyclic bisphenol polyesters are listed in Table 4. Mostof the films were cast from methylene chloride by conventionaltechniques, but a few were cast from chloroform or tetrachloroethane.The films were air-dried and then heated in an oven at 110 C. for 1-2hr. to ensure the removal of all solvent. All films were tough andtransparent.

The inherent viscosities (I.V.) of the polymers were measured in 60/40phenol/tetrachloroethane. The heatdistortion temperatures of the films(2 percent deflection with 50 p.s.i. load) were measured in a forcedconvection oven (ASTM D1637-61). Tensile strengths, not listed, were900015,000 p.s.i. Elongations, also not listed because they depend uponthe film casting conditions, were, for the most part, 530 percent.

Like the polycarbonates, the bisphenol polyesters had very highsoftening pointsabove 300 C. in almost all examplesbut more accuratemeasures of the high-temperature usefulness of polymers are theirsecond-order transition and heat-distortion temperatures. Thesecondorder transition temperatures of the polyesters were determined ononly a few of the polymers, but the heatdistortion temperatures, listedin Table 4, were obtained on all of the polymers.

The diphenyl esters listed in Table 4 are abbreviated as follows:

Diphenyl trans-1,4cyclohexanedicarboxylate'C Diphenyl isophthalate--IDiphenyl dimethylmalonateM Diphenyl sebacateS Diphenyl terephthalateTAll percentages in the table refer to mole percent.

TABLE 4.PROPERTIES OF POLYESTERS FROM POLY- CYCLIC BISPHENOLS DiphenylHeat-Dist. Bisphenol Ester Temp., C.

265 280 (3.. 0.7 260 75% T, 25% I 272 T. 1. 230 I d 40% Brsphenol A. 4.4n0rb0rnyl dene) bis[2,6- T 0. 7 305 d1chlorophenol].4,4-(2-n0rborny1methylene)di- I 0. 8 260 phenol.

g0--. 7 3 S 0.9 285 0 0 0 T 0 0. 6 215 4,4-(2-norbornylmethyle e)bis Io. 29s

[2,6-dich1orophenol]. 4,4'-(3-methyl-2-norbornylmeth- I 0. 9 270ylene)dipheno1.

D0 T 1. 0 279 Do c 0.6 285 4,4-(5,6-d1methyl-2-n0rbornyl- M 0. 7 200methylene)diphenol. 4,4- (hexahydro-t,7-methanoindan- I- 0. 7 275methylene) dlphenol.

D0 T 0.6 285 1130- 7 i 7 S 0.9 278 0 5 ,25 0.7 230 4,hYdro-l,4-exo-5,8-endo- T 0 8 235 drmethanonaphth-Z-ylidene) dlphenol.4,4-(decahydro-1,4:5,8-dimethano- 0. 7 277 naphth-Z-ylmethylene)diphenol. 4,4-(hexahydro-4,7-methanoindan- 1. 0 2655-ylmethylene)-diphenol. 4,4-(hexahydro-4,7-methanoindan-2 I 0. 7 250 or3-ylmethylene)-diphenol.

Do T 0. 8 261 Other properties of the bisphenol polyesters, in generalare similar to those of the polycarbonates: excellent electricalproperties, excellent thermal and oxidative stability at elevatedtemperatures, and relatively slow decrease of tensile strength andtensile modulus with increasing temperature.

The copolyesters are particularly valuable as molding plastics. Some ofthe copolymers exhibit unusually high impact strengths. By usinglong-chain aliphatic dicarboxylic acids it was possible to increase theimpact strengths and lower the heat distortion temperatures to producepolymers suitable for injection molding.

POLYCARBONATES AND POLYESTERS From the foregoing description it isobvious that the polycyclic bisphenol polycarbonates and polyesters ofthis invention possess a very remarkable combination of properties.These polymers have exceedingly high secondorder transition andheat-distortion temperatures-in most cases appreciably higher than anyreported for polycarbonates and polyesters which are soluble in volatilesolvents. Since the polymers are soluble in volatile solvents such asmethylene chloride and chloroform, it is not necessary to process thepolymers at high melt temperatures. Films can be readily obtained bycasting from sol vents, and fibers can be easily obtained bywet-spinning and dry-spinning from solution. The polymers and copolymerswith second-order transition temperatures below 250 C. can be injectionmolded, but it is very difficult to satisfactorily injection-mold thosewith higher transition temperatures.

In the polycarbonate and polyester structures, R and R extend from themain molecular chain and have an iminfluence on molecular alignment andintermolecular attraction. When such side groups protrude from the mainmolecular chain in polyamides and polyesters, the melting points andsecond-order transition temperatures are lowered. Generally, the largerthe side group the greater is the depression of these properties.Schnell, Ind. Eng. Chem., 51, 157 (1959) has pointed out thatasymmetrical substitution lowers the melting range of polycarbonates.Our polycarbonates and polyesters from polycyclic bisphenols, on theother hand, show the opposite effect: the second-order transitiontemperature is increased when the size of the polycyclic side group isincreased.

It is believed that the high second-order transition temperatures ofthese polycyclic bisphenol polymers can be attributed to two factors:(1) the molecular chains are comparatively stitf and rigid and (2) thependant polycyclic groups are three-dimensional in shape. Factor (1): Ascan be demonstrated with models, the two phenyl groups are attached to acarbon atom which has a high degree of steric hindrance. These phenylgroups, therefore, are rigidly attached, much more so than the phenylgroups in the bisphenol A polymers, which have high second-ordertransition temperatures that are attributed 31 to stiffness of themolecular chain. Factor (2): The polycyclic groups are three-dimensionalstructures, and each dimension is appreciable. The norbornane ring, forinstance, has the following structure:

Therefore, a group cannot be oriented in a preferred direction to passthrough a small space between molecular chains as can alkyl, phenyl, orcyclohexyl groups, all of Which have at least one relatively smalldimension. Since softening and melting in polymers is due to themovement of molecular chains, polymers containing three-dimensionalpolycyclic structures have the higher softening points and second-ordertransition temperatures.

Polymers from the halogenated bisphenols have appreciably highersecond-order transition and heat-distortion temperatures than those fromthe unhalogenated bisphenols. It is probable that the halogen atoms arefunctioning both as chain-stiffening agents and bulky side groups, thusadding to the effect of the polycyclic structure.

In the above structure when R, R, and C are part of a cyclohexane ringand X is carbonyl, the polycarbonate has a second-order transitiontemperature of 179 C. as determined by our heat-distortion procedure.[Schnell, Ind. Eng. Chem., 51, 157 (1959) reports 175 C.] When R, R, andC are part of a norbornane ring, on the other hand, the polycarbonatehas a second-order transition temperature of 224 C. When a five-memberedring is fused to the norbornane ring, the second-order transitiontemperature is higher256 C. The transition temperature is even higherwhen a second norbornane ring is fused instead of a cyclopentane ring.

Similarly, when X is isophthaloyl or terephthaloyl, the correspondingbisphenol polyesters have exceptionally high second-order transition andheat-distortion temperatures compared to those in the literautre, suchas in J. Poly. Sci., 40, 399 (1959).

Since the polycyclic bisphenol polycarbonates and polyesters of thisinvention have excellent oxidative and thermal stability, they aresuitable for use in numerous applications requiring stability atelevated temperatures. Since the polymers have exceptional electricalproperties, they are particularly valuable for use as electricalinsulating materials and capacitor dielectrics when operation atelevated temperatures is essential.

Nonburning films, fibers, and plastics can be obtained from thehalogenated polycyclic bisphenols. The plastics which contain no halogenare self-extinguishing without dripping.

Other applications of the invention include utility as photographic filmbase, magnetic tape base, adhesive tape base, sheet packaging materials,protective coatings, molded components for aircraft and space vehicles,nonburning protective clothing, etc.

Although the invention has been described in considerable detail withreference to certain preferred embodiments thereof, it will beunderstood that variations and modifications can be effected withoutdeparting from the spirit and scope of the invention as describedhereinabove and as defined in the appended claims.

We claim:

1. A bisphenol having the general formula:

RI! RI! RI! RI! wherein R" is a member selected from the groupconsisting of hydrogen, halogen and alkyl groups containing from 1 to 4carbon atoms and X is a gem-bivalent radical selected from the groupconsisting of radicals having the following general formulas:

fig c Cu wherein R is selected from the group consisting of hydrogenatoms, halogen atoms, phenyl groups and alkyl groups containing from 1to 4 carbon atoms. 2. A bisphenol having the general formula:

wherein R" is a member selected from the group consisting of hydrogenatoms, halogen atoms and alkyl groups containing from 1 to 4 carbonatoms and X is a gem-bivalent radical having the following generalformula:

wherein R is selected from the group consisting of hydrogen atoms,halogen atoms, phenyl groups and alkyl groups containing from 1 to 4carbon atoms.

3. A bisphenol having the general formula:

wherein R is a member selected from the group consisting of hydrogenatoms, halogen atoms and alkyl groups containing from 1 to 4 carbonatoms and X is a gembivalent radical having the following generalformula:

wherein R is selected from the group consisting of hydrogen atoms,halogen atoms, phenyl groups, and alkyl groups containing from 1 to 4carbon atoms.

4. A bisphenol having the general formula:

wherein R" is a member selected from the group consisting of hydrogenatoms, halogen atoms and alkyl groups containing from 1 to 4 carbonatoms and X is a gembivalent radical having the following generalformula:

wherein R is selected from the group consisting of hydrogen atoms,halogen atoms, phenyl groups and alkyl groups containing from 1 to 4carbon atoms.

5. A bisphenol having the general formula:

wherein R" is a member selected from the group consisting of hydrogenatoms, halogen atoms and alkyl groups containing from 1 to 4 carbonatoms and X is a gem-bivalent radical having the following generalformula:

im M t) \I/ wherein R is selected from the group consisting of hydrogenatoms, halogen atoms, phenyl groups and alkyl groups containing from 1to 4 carbon atoms.

6. A bisphenol having the general formula:

RI! RI! RI! RI! wherein R" is a member selected from the groupconsisting of hydrogen atoms, halogen atoms and alkyl groups containingfrom 1 to 4 carbon atoms and X is a gem-bivalent radical having thefollowing general formula:

Br g P wherein R is selected from the group consisting of hydrogenatoms, halogen atoms, phenyl groups and alkyl groups containing from 1to 4 carbon atoms.

7. A bisphenol having the general formula:.

RI! RU wherein R" is a member selected from the group consisting ofhydrogen atoms, halogen atoms and alkyl groups containing from 1 to 4carbon atoms and X is a gem-bivalent radical having the followinggeneral wherein R is selected from the group consisting of hydrogenatoms, halogen atoms, phenyl groups and alkyl groups containing from 1to 4 carbon atoms.

groups containing from 1 to 4 carbon atoms and X is a gem-bivalentradical having the following general formula:

CH M wherein R is selected from the group consisting of hydrogen atoms,halogen atoms, phenyl groups and alkyl groups containing from 1 to 4carbon atoms.

9. A' bisphenol having the general formula:

wherein R" is a member selected from the group consisting of hydrogenatoms, halogen atoms and alkyl groups containing from 1 to 4 carbonatoms and X is a gem-bivalent radical having the following generalformula:

IR Q on wherein R is selected from the group consisting of hydrogenatoms, halogen atoms, phenyl groups and alkyl groups containing from 1to 4 carbon atoms.

10. A bisphenol having the general formula:

wherein R" is a member selected from the group consisting of hydrogenatoms, halogen atoms and alkyl groups containing from 1 to 4 carbonatoms and X is a gembivalent radical having the following generalformula:

wherein R is selected from the group consisting of hydrogen atoms,halogen atoms, phenyl groups and alkyl groups containing from 1 to 4carbon atoms.

11. A bisphenol having the general formula:

u R" no x 6- on R D a" wherein R" is a member selected from the groupconsisting of hydrogen atoms, halogen atoms and alkyl groups containingfrom 1 to 4 carbon atoms and X is a gembivalent radical having thefollowing general formula:

wherein R is selected from the group consisting of hydrogen atoms,halogen atoms, phenyl groups and alkyl groups containing from 1 to4carbon atoms.

12. A bisphenol having the general formula? wherein R" is a memberselected from the group consisting of hydrogen atoms, halogen atoms andalkyl groups containing from 1 to 4 carbon atoms and X is a gembivalentradical having the following general formula:

wherein R is selected from the group consisting of hydrogen atoms,halogen atoms, phenyl groups and alkyl groups containing from 1 to 4carbon atoms.

13. A bisphenol having the general formula:

nag

wherein R is selected from the group consisting of hydrogen atoms,halogen atoms, phenyl groups and alkyl groups containing from 1 to 4carbon atoms.

14. A bisphenol having the general formula:

wherein R" is a member selected from the group consisting of hydrogenatoms, halogen atoms and alkyl groups containing from 1 to 4 carbonatoms and X is a gembivalent radical having the following generalformula:

wherein R is selected from the group consisting of hydrogen atoms,halogen atoms, phenyl groups and alkyl groups containing from 1 to 4carbon atoms.

15. A bisphenol having the general formula:

wherein R" is a member selected from the group consisting of hydrogenatoms, halogen atoms and alkyl groups containing from 1 to 4 carbonatoms and X is a gembivalent radical having the following generalformula:

wherein R is selected from the group consisting of hydrogen atoms,halogen atoms, phenyl groups and alkyl groups containing from 1 to 4carbon atoms.

References Cited UNITED STATES PATENTS 2,407,508 9/1946 Morris et al260-598 X 2,761,879 9/ 1956 Soloway. 3,298,998 1/1967 McConnell et al.260-619 LEON ZITVER, Primary Examiner N. P. MORGENSTERN, AssistantExaminer US. Cl. X.R.

erg- 1 050 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PatentNo. 3,5 -7, 7 Dazed June 25. 1Q7O Inventor) John R. Caldwell and WinstonJ. Jackson Jr.

It is certified that error appears in the abovc-identified patent andthat said Letters Patent are hereby corrected as shown below:

Column 1, line 19, "proved temperature" should read ---proved hightemperature--- Column 1, line 56, "Agnew" should read ---Angew--- Column2, lines 60-65, the formula should read as shown below:

Column 5, line 17, "inventon" should read ---invention---. Column 8,line 5, "M.P. should read ---m.p.--- Column 8,

line 9, "CH should read ---CH Column 8, line 1 "R-Cl) should read ---R"Cl) Column 9, lines 57- 59, should be changed to read ---mixture andmelted at 222-22 +C.

l'-(3-Phenyl-2-norbornylmethylene)diphenol (XII), R H, R' C H melted atl95-l98C.-

Column 10, line 55, "gorups" should read ---groups---. Column 10', line71, (rem should read (XV, R'J Column 12, line 6, "RA" should read---4,4'---. Column 12, line 62, "5,8'" should read ---5,8---. Column 13,line 29,

"XXIV" should read ---XXIX--- Patent No. g5 b 7 Dated June 23. lQ'YOlnvenmds) John R. Caldwell and Winston J. Jackson. Jr.

It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

Column 15, lines 58-65, the formula should read as shown below:

0 2 OH Q Column 16, lines 45-50, the formula should read as shown below:

Column 17, lines 5-24, the formulas should read as shown below:

ll OH 40 R R@ K2CI'207 2 LII LIII H+

